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Complexes de Ru(II) en tant que sensibilisateur pour les Ln(III) émettant dans l'IR ,
,
, Caractérisation de complexes hétérobimétalliques d-f silylés, Complexes monomères précurseurs et complexes hétérobimétalliques d-f silylés
,
, 236 5.1. Greffage et caractérisation des complexes précurseurs monomères et hétérobimétallique d-f silylés sur la matrice de silice mésoporeuse
,
243 permettent de sensibiliser les ions lanthanides émettant dans l'IR de façon efficace, Des plus l'état excité de ,
, Alternativement, des efforts ont été réalisés pour modifier les ligands 2-2'-bipyridine
Ln(III) et ainsi avoir la possibilité de transfert d'électron et d'énergie efficaces ,
Les complexes bimétalliques d-f obtenus en utilisant des ligands pontants saturés (-CH2CH2-) et des ligands pontant insaturés et conjugués (p-C6H4 et de complexes silylés, monomères et dimères, ont été confirmées par RMN en solution et à l'état solide, spectroscopie infrarouge, UV/Visible, FT-Raman, spectrométrie de masse et analyse élémentaire. Les complexes précurseurs monomères RuL (80 % de rendement) et Ru (85 % de rendement) ont été caractérisés par mesures de CP MAS du 13 C et RMN du 1 H (liquide), respectivement. L'utilisation de différentes séquence RMN a permis d'identifier sans ambiguïté la structure des complexes notamment en présence de ligands bipyridine et bipyrimidine, 28 ont étudiés les processus de transfert d'énergie (EnT) Ru(II)-Ln(III) à partir du chromophores [M(bpy)3] 2+, p.107 ,
et 109, respectivement) montrent distinctement les signaux attribués aux ligands bpy et bpmd, ce qui nous permet de confirmer la structure du complexe proposé. De façon similaire, vol.34, p.111 ,
, Si par RMN du proton il n'a pas été possible de distinguer et d'attribuer les signaux des différents ligands, des mesures de TOCSY 1D (figure 39, pages 115 et 116), HSQC (figure 40, page 117) et HMBC (figure 41, page 118) ont été réalisées et ont permis d'identifier les signaux attribués aux ligands bpy
et 129, respectivement) ont confirmés la présence des différentes fonctions notamment la fonction alkoxysilane par la présence de bandes de vibration caractéristiques, Particulièrement, les bandes ?(Si-O-CH3), ?(O-CH3) et ?(Si-O-C), vol.48, p.126 ,
, Le spectre d'absorption dans la région UV-visible des complexes, mesurés en solution dans l'éthanol
, nm ont été attribuées à la transition 1 TCML (d??*, caractéristiques du Ru vers les ligands bpy, bpy-Si et bpmd), et la bande à 287 nm est attribuée aux transitions ???* des ligands bpy
, Propriétés photophysiques de complexes hétérobimétalliques Ru(II)-Nd/Yb(III) silylés
, Après avoir isolé et entièrement caractérisé les complexes hétérobimétalliques d-f
lorsque l'excitation est faite sur le chromophore Ru(II), l'émission dans ,